DE2017840A1 - - Google Patents

Description

Process for the preparation of fiber-reactive monoazo dyes

The present invention relates to new, valuable fiber-reactive monoazo dyes, processes for their production, their use for dyeing or printing organic material, especially textile material made from natural and regenerated cellulose loose and made from natural and synthetic polyamides, and as an industrial product that uses this new fiber-reactive monoazo dyed or printed organic material. ■

It was found that fiber-reactive monoazo dyes άύτ general formula I:

Y '

N = N

NH- (CO) _n-1 -Py wherein the benzene nucleus

A can be further substituted,
Y the COOH or the SO-jH group,
X the CH ₃ - CCOH, COO low molecular weight alkyl or CONH ^ group,

preferably the CHo group »
Z OH or NF «,, preferably OH,
η the numbers 1 or 2 and
Py is a pyrünidyl radical which has at least one reactive halogen atom,

mean, in addition to great color strength, good fastness properties distinguish.

009852/2079

As further substituents of the benzene nucleus Ä be mentioned for example: halogen atoms such as fluorine ,, chlorine or bromine, · low · = molecular weight alkyl groups such as methyl, Aethy1- or Propylgrteppei low molecular weight alkoxy _s groups such as the methoxy, "Aethoscy · = .or Propoxygrüppe } water-solubilizing. Groups such as the sulfonic acid or carboxylic acid group, the sulfamoyl or carbamoy group, N-mono- or Ν, Ν-di-low molecular weight alkyl substituted sulfonic acid amide or carboxamide groups, N-mono- or N, N- substituted in the low molecular weight alkyl radical di-low molecular weight alkylsulfonic acid amide or alkylcarboxylic acid amide groups, fc low molecular weight alkylsulfonyl groups or optionally substituted arylsulfonyl groups.

The benzene nucleus A is advantageous because of halogen, in particular - = - their chlorine or low molecular weight alkyl or alkoxy groups or one Further substituted sulfonic acid group.

The -NH- (CO) ^ _-1 -Py-GrUpPe is advantageously in the p-position to the pyrazole nitrogen bond.

According to the definition, the pyrimidyl radical Py has at least one ₃ but advantageously several reactive halogen atoms, for example fluorine, chlorine or also bromine. It can carry in position 5 further substituents, in particular halogen atoms such as chlorine or bromine, or the cyano group, the nitro group, W hydrocarbon groups, especially low molecular weight alkyl groups _s as the methyl, ethyl or phenyl group "substituted by halogen, low molecular weight alkyl groups, such as the di- or trifluoromethyl group, the chlorine or bromomethyl group, carboxylic acid or sulfonic acid amide groups optionally substituted on the nitrogen atom, carboxylic acid methyl or ethyl ester groups, low molecular weight alkoxy groups, acy groups, for example the benzoyl group. and alkenyl groups such as the allyl or chlorovinyl group.

Residues of the following pyrimidine compounds, for example, are particularly suitable: 2,4-dichloro-5-cyano-pyrimidine, 2,6-Dichlor ™ A-methyl-S-chloromethyl-pyrimidine »2-methylsulfonyl-4-methyl-5,6 ~ dichloropyrimidine and preferably 2,4-dichloropyrimidine-5- or -ö-carboxylic acid chloride, 2,4,6-trifluoro "5-chloropyrimidine, 2,4,6"

00 9 8 52/207 9

Trichloro- "or 2,4,6-trifluoropyrimidine or 2,4,5,6-tetrachloropyr imidine.

The pyrimidyl Py contains more fiber-reactive> halogen atoms, as are also the primary condensation products in which a halogen atom is reacted with ammonia or a primary or secondary amine _s such as methylamine, ethylamine, N, N-dimethylamine, N, N-diethylamine, or phenylamino, with a metal salt of sulphurous acid, with a metal salt of a negatively ring-substituted phenol or thiophenol or with a metal alkoxide or mereaptide.

These new fiber-reactive monoazo dyes are obtained Formula I according to known processes, for example by adding an amino monoazo dye of the general formula II

(ID

wherein A, Y, X and Z have the meaning given under formula I, with a compound introducing the radical - (CO), -Py below usual acylation converts.

Aminomonoazo dyes of the formula II are known and can be prepared by known methods, for example by customary diazotization and coupling processes of corresponding starting materials or by reduction of corresponding azo dyes of the formula II which have a nitro group instead of the amino group -NHU on the phenyl nucleus bonded to the pyrazole nitrogen, or by saponification of corresponding azo dyes of the formula II, which instead of this amino group -NH _? have an NH-acyl group. These nitro or acylamino monoazo dyes are in turn obtained by customary diazotization and coupling methods.

009852/2079

Suitable compounds which introduce the fiber-reactive substituents - (CO), -Py are, for the case where η is - 2, for example the corresponding acid halides, in particular acid chlorides, of the pyrimidinecarboxylic acids mentioned in the discussion of Py, and for the case that η = 1, for example the pyrimidines which have more than one reactive halogen atom, in particular a chlorine atom or fluorine atom. All of these pyrimidines are known and can be prepared by known methods.

The reaction of the Aminomonoazofärbstoffes of formula II with, the fiber-reactive radical - (CO) i ~ Py introducing compound, carried out in known manner expediently in aqueous medium at temperatures of about 0 ° to 6O ⁰ C, optionally inert in the presence of, Easily removable organic solvents, such as low molecular weight aliphatic ketones, for example acetone, and preferably in the presence of mineral acid blunting agents, such as sodium or potassium carbonate, sodium or potassium hydroxide, di- or trisodium or di- or tripotassium phosphate, sodium or potassium acetate.

After completion of the reaction, the finished fiber-reactive Monoazo dye of the formula I from its suitably previously neutralized solution or suspension with an alkali salt, such as Sodium or potassium chloride, salted out, suctioned off, with aqueous Washed sodium or potassium chloride solution and expediently at elevated temperature and, if desired, at a reduced temperature Print dried.

The new fiber-reactive monoazo dyes of the formula I are yellow powders inrer in the form of alkali metal salts in water are readily soluble even at about 20 ⁰ C. They are suitable for dyeing or printing organic material, especially textile material made from natural and regenerated cellulose, such as rayon, jute, ramie, hemp, and above all cotton, or made from synthetic polyamides such as nylon. Perlon or Banlon, or natural polyamides, such as silk or especially wool, as well as chlorinated wool, in reddish to greenish yellow colors

009852/2079

sound. These materials are dyed or printed with the inventions fiber-reactive monoazo dyes of the formula I by the processes customary for these substrates.

The cellulose material is impregnated or printed at a low temperature, for example at 20 ° -50 ° C., with the optionally thickened dye solution, and the dye is then fixed by treatment with acid-binding agents. Examples of these are sodium carbonate, potassium carbonate, di- and trisodium phosphate, sodium hydroxide and, at temperatures above 50 ^° C., potassium or sodium bicarbonate. Instead of subjecting the impregnated substances to an alkaline aftertreatment, the acid-binding agent can preferably be in the form of alkali carbonates in many cases also add to the impregnation liquors or printing pastes and then cause the coloration to develop by briefly heating or steaming to temperatures of approx. 100 ° C. to 160 ° C. or, advantageously, by storing them for a longer period at room temperature and printing pastes are advantageous in this process, for example the addition of urea in amounts of 10 to 200 g per liter of colorant.

One can also the Celluiosematerial with the novel fiber-reactive monoazo dye even after the exhaust process by the in which an acid-binding agent and optionally also salts neutral to be dyed Celluiosematerial such as Natriumchlprid or sodium sulfate-containing dye bath at a long liquor and slightly elevated temperature introduces -, * - the dyeing bath at temperatures of 40, 60 or heated to 100 ° C and leads the dyeing process at that temperature. The exhaustion of the dyestuff besehleunigenden neutral salts can the bath gewünschtenfalIs also rich only after the actual dyeing temperature it is added.

By the treatment with acid-binding agents, the 'new fiber-reactive monoazo dyes are chemically bonded to the fiber. The cellulose dyeings obtained in this way are used for

009862/2079

removal of non-fixed dye then expediently still soaped.

When hot, natural and synthetic polyamide fibers are often made from neutral to weakly acidic, e.g. acetic acid Bath colored. Often the addition of basic nitrogen-containing compounds, such as fatty acid-alkanolamine-ethylene oxide condensation products, or of polyquaternary ammonium compounds, as well as salts such as sodium chloride or sulfate, indicated, The polyamide dyeings of a post-treatment are advantageous with mineral acid binding agents such as ammonia, disodium phosphate, sodium bicarbonate or hexamethylenetetramine, subject.

The cellulose and polyamide dyeings obtained in this way are pure and strongly colored, excellent wetfast, especially washable, water, sweat, alkali and rubbing fast, as well as good light fast. The colored material also has a high level of fibers and surfaces on. Furthermore, the color tone and the lightfastness of the cellulose dyeings and prints obtained are determined in the aftertreatment only marginally influenced by agents that improve crease resistance. By doing all of the above at the same time combine valuable properties, they are superior to the closest comparable known reactive dyes.

Further details are given in the examples below without restricting them to it. The temperatures are given in degrees Celsius. In the dye forms is in each case the free acid form -SOoH indicated, · the dyes, however, are conveniently in the form of their salts, especially theirs Alkali metal or ammonium salts.

009862/2079

. . 20T784Q

example 1

SO-H COOH H ₃ C- = N VL

Ν— (/ \ - NH-CO-

OH CiI

49.7 g of the monoazo dye obtained by coupling diazotized 2-amino-l-carboxy-benzene-5-sulfonic acid with l- (4'-nitrophenyl) -3-methyl-5-pyrazolone-2'-sulfonic acid and then reducing the Nitro group to amino group with sodium sulfide, are dissolved in 300 ml of water at 20-25 ° with 15% aqueous sodium hydroxide solution at a pH of 6.0 to 6.5. The resulting solution is cooled to 0-5 ° by adding crushed ice and 23.3 g of 2,4-dichloropyrimidine-5-carboxylic acid chloride are then added dropwise with stirring. The released during the reaction is neutralized with hydrochloric acid 157 _o aqueous sodium hydroxide solution continuously, wherein the pH of the reaction mixture should be 0 to 6.5 * 6 constantly. As soon as no free amino groups are no longer detectable, the new reactive dye of the above formula with sodium chloride is precipitated, filtered off, washed with dilute Natriumchloridlö'sung in vacuo at 60 ⁰ .65 dried. It is a yellow powder that dissolves in water with a yellow color.

The new reactive dye especially dyes cotton or also textile material made of natural polyamide among those customary for reactive cotton dyes or acidic reactive wool dyes Methods in very lightfast and wetfast greenish yellow shades .

Fiber-reactive monoazo dyes with similar properties are obtained if the aminomonoazo dyes listed in Table I, column 2 below, are used in accordance with the information of Example 1 with the acylating agents listed in column 3 at the temperatures indicated in column 4. The color tones of the corresponding dyeings on cotton or wool are indicated in column 5.

009852/2079

- 8 TABLE X

Example!
No.

Aminoaonoazo dye

Acylation title

temperature

Color ajf Aolle hu. Baii

OOH

^C1

SO ₃ H

do

do 0 T

Cl

"Λ"

Cl Cl ^. Cl

do ly K Cl

Cl-CO _Λ Cl

do

Cl

CO-Cl

TrCOOH

SO H \ 1γ ti Cl

10-15

20-25 °

40- «

40- «

0-5 ^u

0-5 ^υ

greenish yellow

do

do

do

do

reddish yellow

009852/2079

Continuation from Table I.

Example Kr.

AsiinoRonoaiofarbsioff

COOH

<; - / "V HJi .τ

Acyl grounding agents

¹ HJ11-rrCH

SO-H HO

• ^S0 3 ^H

do

SO-H

H = H -, --- τ- CH,

Λη> HO ι SOY

SO ₃ H

COOH HO ι SO-H

NH _n

do

CO-Cl

«Ν

Temperature

do

Cl

do

CO-CI

Cl

egg

Cl 0-5 ^u

10-15 "

10-15 *

0-5 *

Shade ajf soil up. cotton

greenish yellow

do

do

do

do

do

008882/2079

BATH ORIGINAL.

201784

Continuation from Table I.

example

Äßimrionoazo dye

Acyl grounding agents

Temperature hue on col

tt «,

tt «,

HO S

Jl

f! = N -τ; - | - COOH

, _r SO H.
Il 3

.SOJ

NH '.

do

do

SO ₃ H

HO

CH,

SO ₃ H

ryy

ei X -ei

Cl

CO-C!

Y C]

Cl Cl-CO ^ Cl

F ^{?] L} F

do 20-25

40- «

0-5 ^u

40-45 °

0-5 "

* 10-15 °

10-15 "

greenish yellow

reddish yellow

greenish yellow

do

do

do

do

009852/2079 BAD OPIiGiNAL

Continuation from Table I.

Example! Cr.

EraJnorionoazofarbsioff

Acylation moieties

Temperature shade to «great bzs. Ba- ^ iöl Ie

20th

OH

Br

Cl

HO L · SO ₃ H

^S0 3 ^H

Cl

HO '' '

-SO H

22nd

23

JO ₃ H

..SO ₃ H

SO ₃ H

CH ₃ -SO ₂ - ^> -N = Nn-T ₇ CH

VA-

CH ³

CH. P Cl

20-25

20-25 20-25

20-25

green yellow

do

do

do

009862/2079

Continuation from Table I.

Example no.

Ami noraonoazo dye

Acyl grounding agent

temperature

Color on wool or cotton

28

SO ₃ H

so,

SO ₃ H

2 \ =

HO

SOY

HO

SO ₃ H

SO ₃ H

CH,

^N CH "CHJH ^{1 <Γ} ^ ^r

Cl

do

do

do

10-15 "

do

do

do

do

greenish

yellow

do

do

do

do

009862/2079

BATH

Example 2 SO ₀ H

V-NH

48.2 g of the monoazo dye obtained by coupling diazotized 1-amino-4-methoxybenzene-2-sulfonic acid with 4'-acetylamino-1-phenyl-3-methyl-5-pyrazolone-2'-sulfonic acid and subsequent saponification the acetylamino group are dissolved in 300 ml of water at 20-25 ° with 157 aqueous sodium hydroxide solution _o at a pH of 6.0-6.5. The solution is cooled to 10-15 ° by adding ice. 18.5 g of 5-chloro-2,4,6-trifluoropyrimidine are then added dropwise over the course of 1 hour. The pH of the solution is maintained by adding 107 ₀ aqueous sodium hydroxide solution to 6.0-7.0. As soon as the reaction has ended, the new reactive dye of the above formula is precipitated with sodium chloride, filtered off, washed with dilute sodium chloride solution and dried in vacuo at 60-70 °.

The new reactive dye dyes cotton and especially wool or synthetic polyamide fibers for reactive dyes usual methods in very wetfast reddish yellow Shades.

Fiber-reactive monoazo dyes with similar properties are obtained if one of the following table II Column 2, listed aminomonoazo dyes according to the information of Example 2 with the acylating agents listed in column 3 at the temperatures indicated in column 4. The. Color shades of corresponding coloring on cotton or Wool are indicated in column 5.

009852/2079 o _{RleiNAL INSPEC7ED}

- 14 TABLE II

Example
Mr. Ani nononoazo dye ² ? 0 ₃ H Acylierur.gs-
nittel i temperature Color on col
or BaWoIIe SO H do Cl 1 • 10-15 ° yellow Hit? 'SOY
- ftf F. do CO-Cl Z J * Y Cl 0-5 ° do ' Cl 3 I.
Cl
- M ¹ ' reddish
yellow 4th V '20-25 ° do 1
F. S. do 10-15 ° greenish
yellow

60ltti / 2P7t

BATH ORIGINAL

Continuation from Table II

example
Kr. CH ₃ - Ali noionoazof srbsio.i f SO.H
ι 3 rri . AcyMeruros-
aUtel i temperature 10-15 ° Shade on nolle
bzs. Build-should ' SO ₃ H V 1 6th N greenish ■
yellow ■ ^CH 3 ~ HO 5
O 0-5 ° CO-Cl 7th NH ₂ ii. ii
Ύ
Cl do. < ⁼ hX "· 10-15 ° ύ F JLf 8th I.
NH y ^F •do ^ SO ₃ H * CH ₃
SO ₀ H
/ 3 2

009852/2079

Example 3

C ₂ H ₅ -O

OH Cl 49.6 g of the monoazo dye obtained by coupling diazotized l-amino-4-ethoxybenzene-2-sulfonic acid with 4'-acetylamino-1-phenyl-3-methyl-5-pyrazolone-2'-sulfonic acid and subsequent saponification of the acetylamino group are in 300 ml of water - from 20-25 ° with 15% aqueous sodium hydroxide solution for one _ pH value of 6.0-6.5 dissolved. The solution is made by adding ice ™ cooled to 10-15 °. Then 18.5 g are added dropwise within 1 hour 5-chloro-2,4,6-trifluoropyrimidine. The pH of the solution is increased by adding 10% aqueous sodium hydroxide solution 6.0-7.0 held. As soon as the reaction has ended, the new reactive dye of the above formula is precipitated with sodium chloride, filtered off, washed with dilute sodium chloride solution and dried in vacuo at 60-70 °.

The new reactive dye dyes cotton and in particular Wool or synthetic polyamide fibers using methods customary for reactive dyes in very wetfast yellow shades.

^ Example 4 '

A cotton fabric is padded with a solution containing 20 g of the reactive dye according to Example 1 per liter of water, padded at 20-25 °, squeezed off to a liquid absorption of 80% and dried at 100 ° for 1 minute. The goods pretreated in this way are then padded with a solution containing 250 g of sodium chloride and 15 g of 30% aqueous sodium hydroxide solution per liter of water, squeezed to a liquid absorption of 80% and then for 10-30 seconds at 20-25 ° ^C Exposed to air. It is then soaped for 10 minutes in a bath containing 2 g of soap per liter at 95-98 °, then rinsed and dried. A greenish yellow, very good wet and lightfast cotton dye is obtained *

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Example 5

A printing paste is made by adding 330 ml of water, 20Og urea, 10 g of the sodium salt of m-nitrobenzenesulfonic acid, 395 g sodium alginate thickening 5% and 25 g sodium bicarbonate at room temperature (20 °) to a stock thickening stirred and stirred into this thickening 40 g of the reactive dye according to Example 1.

If this printing paste is used to print a cotton fabric and steams the dried fabric for 60 seconds at 101-103 °, soaps, rinses and dries, the result is a yellow, very wet and lightfast print.

Example 6

In a dye bath of 40 °, which is in 4000 ml of water, 1.5 g Reactive dye according to Example 1 of Table I, 6 g of 40% strength Acetic acid, 4 g ammonium sulfate, 5 g sodium sulfate and 0.5 g contains a polyoxyethylene stearylamine, 100 g of a woolen fabric are added. The dyebath is heated within 30 minutes to the boil and keep it at this temperature for an hour. After washing and drying the wool fabric, it is obtained one level greenish yellow, excellent washing, sweat- and lightfast wool dye.

t * - '· - 009852 / ^ 079

Claims (13)

Claims 1. A fiber-reactive monoazo dyes of the general formula I Nk- (OO) _n-1 -Py in what formula the benzene nucleus A can be further substituted, Y the COOH or the SO-H group, X is the CH ₃ , COOH, COO low molecular weight alkyl or CONH ₂ group, Z OH or NH _£ ,
η the numbers 1 or 2 and
Py is a pyrimidyl radical, which is at least one reactive Has halogen atom _s
mean. 2. Fiber-reactive monoazo dyes of the general formula I according to claim 1, characterized in that the benzene nucleus A is further substituted by halogen atoms, low molecular weight alkyl or alkoxy groups or by a sulfonic acid group. 3. Fiber-reactive monoazo dyes of the general formula I. according to claims 1 and 2, characterized in that X is the Methyl group and Z represents the hydroxyl group. 4. Fiber-reactive monoazo dyes of the general formula I according to claims 1 to 3, characterized in that the group -NH- (CO) ι-Py is in the p-position to the pyrazole nitrogen bond. 0OB «2/2079 or _{IGINAL INSPECTED} -; ₁₉ - 2Ό17840 5. Fiber-reactive monoazo dyes of the general formula I. according to claims 1 to 4, characterized in that η = 2 and Py is the 2,4-dichloropyrimidine-5- or -6-carbonyl radical represents. \ 6. Fiber-reactive monoazo dyes of the general formula I. according to claims 1 to 4, characterized in that η = 1 and Py is the 2,4-difluoro-5-chloro-pyrimidyl-6 radical or the ^ Represents 2,4,5-trichloropyrimidyl-6 radical. 7. A fiber-reactive monoazo dye according to claim 1 i the formula XOOH. 8. A fiber-reactive monoazo dye according to claim 1 the formula X) OH 009862/2079 orig, nal! NspeAted 9. A fiber-reactive monoazo dye according to claim dor formula ^N " 10. A fiber-reactive Monoazof arbs toff according to claim the formula CH. 11. Process for the production of fiber-reactive monoazo dyes, characterized in that one uses an amino monoazo dye of the general formula II N = N Z (II) O ₃ H with a compound introducing the residue - (CO) _j-Py to a fiber-reactive monoazo dye of the general formula I 009852/2079 BATH ORIGINAL NH- (CO) _n-1 -Py. implements the formulas in which a benzene nucleus A can still be substituted with pus, Y dia COOH or the SO- ^ l group, K the CHj-, COOH-, COO-low molecular weight alkyl, or CONH ^ group Z OH or NH _7. ,
η the numbers 1 or 2 and
Py a Py liii idyl residue, which is at least one reactive Has halogen atom,
mean. 12. A method for dyeing or printing organic material, characterized in that .that fiber-reactive .monoazo dyes are used the general formula I given in claim 1 is used. 13. Process for dyeing or printing textile material made of cellulose or polyamide, characterized in that fiber-reactive monoazo dyes of those specified in claim 1 are used general formula I used. .14. That using the fiber-reactive monoazo dyes according to claim 1 colored or printed organic material. Ll, '). 70 BATH ORIGINAL